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US8329796B2 - Mixtures of diisononyl esters of terephthalic acid, method for the production thereof and use thereof - Google Patents

Mixtures of diisononyl esters of terephthalic acid, method for the production thereof and use thereof Download PDF

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US8329796B2
US8329796B2 US12/811,163 US81116308A US8329796B2 US 8329796 B2 US8329796 B2 US 8329796B2 US 81116308 A US81116308 A US 81116308A US 8329796 B2 US8329796 B2 US 8329796B2
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esters
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Michael Grass
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Evonik Operations GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/80—Phthalic acid esters
    • C07C69/82—Terephthalic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic

Definitions

  • the invention relates to diisononyl terephthalate mixtures, i.e. diisononyl esters of terephthalic acid, which take the form of isomer mixtures, in which the isomeric nonyl moieties in the ester mixture have a particular degree of branching.
  • the present invention also relates to the use of these mixtures and to a process for their production.
  • Polyvinyl chloride is one of the polymers of greatest commercial importance. It is widely used in the form of either rigid or flexible PVC.
  • plasticizers are added to the PVC, and those used in most cases are phthalic esters, in particular di-2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP) and diisodecyl phthalate (DIDP).
  • DEHP di-2-ethylhexyl phthalate
  • DIDP diisononyl phthalate
  • DIDP diisodecyl phthalate
  • terephthalic acid PTA
  • DMT dimethyl terephthalate
  • PET polyethylene terephthalate
  • DEHT di-2-ethylhexyl terephthalate
  • diesters of phthalic acid in particular di-2-ethylhexyl phthalates, are metabolized differently from the diesters of terephthalic acid.
  • the terephthalates are first completely hydrolyzed to give alcohol and terephthalic acid, whereas the phthalates are only hydrolyzed to give the monoester.
  • di-2-ethylhexyl phthalate and di-2-ethylhexyl terephthalate are metabolized differently, di-2-ethylhexyl terephthalate has, according to James L. Cooper, markedly lower toxicity than di-2-ethylhexyl phthalate.
  • terephthalates like the phthalates, can be produced via a one-stage esterification reaction starting from readily available raw materials, with no need for any additional hydrogenation stage. Conversion of the production process to terephthalates therefore results in only a low level of requirement for necessary changes to production plants, and no capital expenditure on plant for a hydrogenation stage.
  • esters of terephthalic acid and isononanol i.e. a mixture of branched and, if appropriate, linear nonyl alcohol(s), and nor have these been marketed as plasticizers hitherto.
  • the object of the present invention consisted in provision of diisononyl terephthalates which have good suitability as plasticizers, in particular for the plasticizing of PVC.
  • the action of a plasticizer consists in reducing the glass transition temperature of the plastic to be plasticized sufficiently that it retains adequate flexibility at service temperatures. The intention is therefore that the glass transition temperature of the material be below the service temperature. Suitable diisononyl terephthalates should therefore exhibit the lowest possible glass transition temperature.
  • the glass transition temperature for DEHP will be used as guideline value here and is about ⁇ 80° C. (determined by means of differential scanning calorimetry, DSC).
  • mixtures of isononyl terephthalates which comprise at least two constitutionally different nonyl moieties and whose average degree of branching is from 1.0 to 2.2 are liquid even at low temperatures down to about ⁇ 70° C. and exhibit glass transition temperatures below ⁇ 70° C.
  • These isononyl terephthalates therefore have particularly good suitability as plasticizers, in particular as plasticizers for PVC.
  • the invention therefore provides mixtures of diisononyl esters of terephthalic acid in which the average degree of branching of the isomeric nonyl moieties in the ester mixture is from 1.0 to 2.2.
  • the invention further provides a process for the production of mixtures of diisononyl esters of terephthalic acid, characterized in that the production process uses a mixture of isomeric nonanols whose average degree of branching is from 1.0 to 2.2.
  • the invention also provides the use of the inventive mixtures as plasticizer or part of a plasticizer composition in plastics or components of plastics, or as additive in paints or in coatings, or in adhesives or components of adhesives, or in sealing compositions, or as solvent.
  • the invention provides plastics and plastics compositions, in particular based on PVC, PVB or PAMA, which comprise the inventive mixtures of diisononyl esters of terephthalic acid, and also provides plastics products produced from these compositions.
  • the inventive mixtures of diisononyl esters of terephthalic acid are characterized in that the degree of branching of the isononyl moieties of the diisononyl esters present in the mixture is from 1.0 to 2.2, preferably from 1.1 to 2.1.
  • a particularly preferred degree of branching is from 1.1 to 2.0, and in particular from 1.2 to 1.5.
  • the isononyl moieties here are based on primary nonyl alcohols.
  • 1 H NMR methods or 13 C NMR methods can be used to determine the average degree of branching of the isononyl moieties in the terephthalic diester mixture.
  • the spectra are recorded by way of example by dissolving 20 mg of substance in 0.6 ml of CDCl 3 (comprising 1% by weight of TMS) and charging the solution to an NMR tube whose diameter is 5 mm.
  • Both the substance to be studied and the CDCl 3 used can first be dried over molecular sieve in order to exclude any errors in the values measured due to possible presence of water.
  • the method of determination of the degree of branching is advantageous in comparison with other methods for the characterization of alcohol moieties, described by way of example in WO 03/029339, since water contamination in essence has no effect on the results measured and their evaluation.
  • any commercially available NMR equipment can be used for the NMR-spectroscopic studies.
  • the present NMR-spectroscopic studies used Avance 500 equipment from Bruker.
  • the resultant 1 H NMR spectra of the mixtures of diisononyl esters of terephthalic acid have, in the range from 0.5 ppm as far as the minimum of the lowest value in the range from 0.9 to 1.1 ppm, resonance signals which in essence are formed by the signals of the hydrogen atoms of the methyl group(s) of the isononyl groups.
  • the signals in the range of chemical shifts from 3.6 to 4.4 ppm can essentially be attributed to the hydrogen atoms of the methylene group adjacent to the oxygen of the alcohol or of the alcohol moiety.
  • the results are quantified by determining the area under the respective resonance signals, i.e. the area included between the signal and the base line.
  • each of the intensities has to be divided by 3 and, respectively, 2 in order to obtain the ratio of the number of methyl groups to the number of methylene groups adjacent to an oxygen atom, in the isononyl moiety. Since a linear primary nonanol which has only one methyl group and one methylene group adjacent to an oxygen atom contains no branching and accordingly must have a degree of branching of 0, the quantity 1 then has to be subtracted from the ratio.
  • I(CH 3 ) means area integral essentially attributed to the methyl hydrogen atoms
  • I(OCH 2 ) means area integral for the methylene hydrogen atoms adjacent to the oxygen atom.
  • the nature and number of the alcohol moieties present in the diisononyl ester mixtures can also be determined by saponifying the ester in basic solution and then analyzing the alcohol by GC. Care has to be taken here that the GC conditions (in particular column material and column dimensions, and also temperature profile) permit separation of the alcohols into the individual isomers.
  • the isomeric nonanols or isononanol mixtures to be used in the inventive process for the production of these mixtures of diisononyl esters of terephthalic acid can generally be produced by hydroformylation of octenes, which in turn can be produced in various ways.
  • the raw material generally used for the production of the octenes comprises industrial C 4 streams, which initially can comprise all of the isomeric C 4 olefins, alongside the saturated butanes and sometimes impurities such as C 3 and C 5 olefins and acetylenic compounds.
  • Oligomerization of this olefin mixture gives mainly isomeric octene mixtures, alongside higher oligomers such as C 12 and C 16 olefin mixtures.
  • These octene mixtures from which the higher oligomers have preferably been removed by distillation, are hydroformylated to give the corresponding aldehydes, and then hydrogenated to give the alcohol.
  • octene mixtures that can be used are those obtained by way of what is known as the polygas process, in which C 3 /C 4 mixtures are oligomerized on a solid acidic catalyst, preferably on a solid phosphoric acid catalyst (SPA process).
  • SPA process solid phosphoric acid catalyst
  • the nonanols obtained by these processes generally also comprise octanols and decanols, and sometimes also undecanols, and the average chain length here can therefore deviate from 9 carbon atoms. This has no effect on the determination of the degree of branching B by the abovementioned method, however.
  • this C 9 -rich C 5 -C 11 alcohol mixture is markedly more complex, and attribution of the individual peaks in the corresponding gas chromatograms cannot be achieved without enormous additional cost.
  • a characteristic of this mixture is that the proportion of n-nonanol is generally markedly below two percent.
  • a distribution in typical products of this type has from 2 to 6% of octanols, from 70 to 78% of nonanols, from 15 to 25% of decanols and at most 2% of undecanols.
  • the boiling range (start of boiling to dry point) is from 202° C. to 219° C. at atmospheric pressure.
  • the EU Risk Assessment on diisononyl phthalate from the polygas process (DINP 1, CAS no.
  • the degree of branching of nonanol mixtures of this constitution is generally from 1.4 to 2.2 according to the abovementioned method, in particular from 1.5 to 2.0, and particularly typically from 1.6 to 1.9.
  • mixtures which can be used in the inventive process and comprise isomeric nonanols are those obtainable via hydroformylation of a mixture of isomeric octenes and subsequent or simultaneous hydrogenation.
  • the mixture of isomeric octenes here is obtained by bringing a hydrocarbon mixture comprising butenes into contact with an oligomerization catalyst, in particular with a catalyst formally comprising nickel oxide.
  • the proportion of isobutene in the hydrocarbon mixture is preferably smaller than 20% by weight, with preference smaller than 10% by weight, particularly preferably smaller than 5% by weight, very particularly preferably smaller than 3% by weight, with particular preference smaller than 1% by weight, preferably from 0.01 to 1% by weight and with particular preference from 0.05 to 0.5% by weight, based on the butenes.
  • the preparation of isomeric octenes via oligomerization of essentially linear butenes on supported nickel catalysts is known by way of example as the OCTOL process, which is described by way of example in EP 0 395 857 or EP 1 029 839.
  • the mixtures of isomeric octenes are then fed to a hydroformylation process.
  • the hydroformylation process can take place in the presence of modified or unmodified cobalt catalysts or modified or unmodified rhodium catalysts.
  • the hydroformylation process preferably takes place in the presence of unmodified cobalt compounds.
  • the hydroformylation process is usually followed by a hydrogenation process. These hydroformylation/hydrogenation processes are known by way of example from EP 0 850 905 and EP 1 172 349.
  • the hydroformylation process can also take place in the presence of rhodium catalysts. These hydroformylation processes are well known.
  • the degree of branching of nonanol mixtures of this constitution is generally from 1.1 to 1.4, in particular from 1.2 to 1.3.
  • catalysts comprising nickel by way of example, catalysts comprising Ti or comprising Zr are used for the production of the octene mixture.
  • catalysts comprising Ti or comprising Zr are described by way of example in EP 1 171 413.
  • the degree of branching of isononanol mixtures of this constitution is generally from 1.0 to 1.4, in particular from 1.2 to 1.3.
  • the mixture of isomeric nonanols used in the inventive process can also comprise a mixture obtained via mixing of isomerically pure nonanols and/or fractions of a plurality of isomeric nonanols.
  • a large number of isomerically pure nonanols is commercially available.
  • Nonanol mixtures or nonanol fractions are equally commercially available which do not have the properties preferred for the inventive process.
  • Simple mixing of these isomerically pure nonanols with nonanol mixtures can produce mixtures of nonanols which have the desired average degrees of branching and which provide terephthalic diester mixtures with the properties demanded.
  • the isononyl alcohol mixtures to be used ideally comprise no more than from 0.0001 to 10 mol % of 3,5,5-trimethylhexanol.
  • the mixture preferably comprises less than 5 mol %, in particular less than 1 mol % and particularly preferably less than 0.5 mol %, of 3,5,5-trimethylhexanol.
  • the proportion of n-nonanol in the isononyl alcohol mixture to be used is from 0.001 to 20 mol %, preferably from 1 to 18 mol % and particularly preferably from 5 to 15 mol %.
  • the contents of 3,5,5-trimethylhexanol and of n-nonanol in the alcohol mixture can be determined conventionally by gas-chromatographic analysis methods (GC).
  • GC gas-chromatographic analysis methods
  • Nonyl alcohol mixtures obtained via saponification of the inventive diisononyl esters preferably comprise from 0.001 to 20 mol %, preferably from 0.5 to 18 mol %, particularly preferably from 6 to 16 mol %, of unbranched nonanols (i.e. n-nonanol).
  • These mixtures moreover comprise from 5 to 90 mol %, preferably from 10 to 80 mol %, particularly preferably from 45 to 75 mol %, of nonanols having branching, and also from 5 to 70 mol %, preferably from 10 to 60 mol %, particularly preferably from 15 to 35 mol % of doubly branched nonanols, and, finally, from 0.1 to 15 mol %, preferably from 0.1 to 8 mol %, particularly preferably from 0.1 to 5 mol %, of triply branched nonanols.
  • these nonanol mixtures can also comprise from 0 to 40 mol %, preferably from 0 to 30 mol %, particularly preferably from 0.1 to 6.5% by weight, of other components.
  • Other components are generally octanols, decanols or nonanols more than triply branched, where the entirety of all of the components mentioned gives 100 mol %.
  • the inventive mixtures of diisononyl terephthalates can be produced by the following methods:
  • the inventive mixtures of isomeric dinonyl terephthalates are preferably produced by methods a) and b).
  • diisononyl terephthalate is produced by transesterification
  • a preferred starting material is dimethyl terephthalate (DMT), which is produced on a large industrial scale.
  • the transesterification process is carried out catalytically, for example using bases or Lewis acids or Brönstedt acids as catalyst. Irrespective of which catalyst is used, a temperature-dependent equilibrium always becomes established between the starting materials (dialkyl terephthalate and isononanols) and the products (diisononyl terephthalates and alcohol liberated from the dialkyl terephthalate used). In order to shift the equilibrium in favour of the inventive terephthalic ester, it can be advantageous to use distillation to remove, from the reaction mixture, the alcohol deriving from the starting ester.
  • the excess used of the starting alcohol is preferably from 5 to 50%, in particular from 10 to 30%, of the molar amount needed for formation of the inventive dialkyl terephthalate.
  • the transesterification catalysts used can comprise acids, such as sulphuric acid, methanesulphonic acid or p-toluenesulphonic acid, or metals or compounds of these.
  • acids such as sulphuric acid, methanesulphonic acid or p-toluenesulphonic acid, or metals or compounds of these.
  • suitable metals or compounds of these are tin, titanium and zirconium, which are used in the form of finely divided metals or advantageously in the form of their salts, or as oxides or in the form of soluble organic compounds.
  • the metal catalysts are high-temperature catalysts whose full activity is often achieved only above 180° C.
  • metal catalysts based on metals or compounds of these can be advantageous to use these metal catalysts based on metals or compounds of these, since it has been found that these catalysts are better than catalysts based on protic acids in leading to less formation of by-products, such as olefins from the alcohol used.
  • metal catalysts whose use is particularly preferred are tin powder, stannous oxide, stannous oxalate, titanic esters, such as tetraisopropyl orthotitanate or tetrabutyl orthotitanate, and also zirconium esters, such as tetrabutyl zirconate.
  • basic catalysts such as oxides, hydroxides, hydrogen carbonates, carbonates or alcoholates of alkali metals or of alkaline earth metals.
  • Alcoholates can also be produced in situ from an alkali metal and a nonanol or an isononanol mixture. It is particularly preferable to use alcoholates whose alcohol moiety is identical with that of one of the alcohols involved in the reaction.
  • the catalyst concentration can be varied widely and in particular as a function of the nature of the catalyst.
  • the catalyst concentration is preferably from 0.005 to 2.0% by weight, based on the reaction mixture.
  • the ideal concentrations for each catalyst can readily be determined by preliminary experiments and are obtained from a compromise between minimum catalyst usage (i.e. cost) and maximum reaction rate.
  • the particularly preferred titanium compound tetrabutyl orthotitanate the preferred concentration is by way of example in the range from 0.05 to 1% by weight, based on the dialkyl terephthalate used.
  • the transesterification process is preferably carried out at a temperature of 100 and 220° C.
  • the temperature is particularly preferably selected to be sufficiently high to permit distillative removal, from the reaction mixture, of the alcohol deriving from the starting ester, at the prescribed pressure.
  • any of the known processes can be used for the production of the inventive mixtures of dinonyl terephthalate by esterification of terephthalic acid using a mixture of primary nonanols.
  • the esterification step preferably takes place by a process in which the water of reaction is removed by azeotropic distillation with the alcohol and the amount of liquid removed from the reaction by the azeotropic distillation is completely or to some extent replaced by the alcohol.
  • amount of liquid is used hereinafter for the volume of liquid removed from the reaction by azeotropic distillation, mainly composed of water of reaction and alcohol. Complete replacement of the amount of liquid removed is preferred. This can by way of example be achieved by level-controlled feed of alcohol into the reactor.
  • the amount of liquid removed is replaced only partially, for example only the alcohol being replaced, while the amount of water of reaction removed is not replaced, but the proportion replaced is always more than 90%, preferably from 95 to 98%.
  • the proportion of the amount of liquid removed that is replaced by alcohol is from 110 to 100%, preferably from 105 to 100%.
  • An advantage of this embodiment of the esterification process is that the reaction rate is increased in comparison with known batch processes. The result can be a shorter cycle time, thus achieving higher space-time yield.
  • esterification process carried out can be an autocatalyzed or catalyzed reaction.
  • Esterification catalysts which can be used are Lewis acids and Brönstedt acids or organometallic substances, which do not necessarily have to act as an acid.
  • Preferred esterification catalysts are alcoholates, and carboxylic salts or chelate compounds of titanium or zirconium, where the catalyst molecule can comprise one or more metal atoms.
  • tetra(isopropyl) orthotitanate and tetra(butyl) orthotitanate are used.
  • the esterification process is preferably carried out in a reaction vessel in which the reaction mixture can be intimately mixed with the aid of a stirrer or of a circulating pump.
  • the starting materials and the catalyst can be charged to the reactor simultaneously or in succession. If one of the starting materials is solid at the charging temperature, it is advantageous to use the liquid starting component as initial charge. Solid starting materials can be fed in the form of powder, granules, crystals or melt. In order to shorten the batch time, it is advisable to start heating during charging.
  • the catalyst can be introduced in pure form or as solution, preferably dissolved in one of the starting materials, at the start or only after the reaction temperature has been reached.
  • the alcohol to be reacted serves as entrainer and can be used in stoichiometric excess.
  • the catalyst concentration depends on the nature of the catalyst. In the case of the titanium compounds whose use is preferred, this is from 0.005 to 1.0% by weight, based on the reaction mixture, in particular from 0.01 to 0.3% by weight.
  • the reaction temperatures are from 160° C. to 270° C.
  • the ideal temperatures are dependent on the starting materials and on the progress of the reaction, and on the catalyst concentration. They can readily be determined experimentally for any particular case. Higher temperatures increase the reaction rates and favour side-reactions, for example water cleavage from alcohols or formation of coloured by-products.
  • side-reactions for example water cleavage from alcohols or formation of coloured by-products.
  • a requirement is that the alcohol can be removed from the reaction mixture by distillation.
  • the desired temperature or the desired temperature range can be adjusted via the pressure in the reaction vessel.
  • the amount of liquid to be returned to the reaction can be composed to some extent or entirely of alcohol obtained via work-up of the azeotropic distillate. It is also possible to carry out the work-up at a later juncture and to use, entirely or to some extent, fresh alcohol, i.e. alcohol provided in a feed vessel, to replace the amount of liquid removed. In other embodiments of the esterification process, the liquid removed is worked up to give the alcohol, preferably to give the pure alcohol.
  • the reaction mixture which is composed essentially of full ester (desired product) and of excess alcohol, comprises not only the catalyst and/or products produced from the catalyst but also small amounts of ester carboxylic acid(s) and/or unreacted carboxylic acid.
  • the excess alcohol is removed, the acidic compounds are neutralized, and the catalyst is destroyed, and the solid by-products produced in the process are removed.
  • Most of the alcohol is removed here by distillation at atmospheric pressure or in vacuo.
  • the final traces of the alcohol can by way of example be removed by steam distillation, in particular in the temperature range from 120 to 225° C. Removal of the alcohol can by way of example be the first or last step of the work-up.
  • the neutralization of the acidic substances can take place via addition of basic compounds of the alkali metals and of the alkaline earth metals. These can be used in the form of their carbonates, hydrogen carbonates or hydroxides.
  • the neutralizing agent can be used in solid form or preferably as solution, in particular as aqueous solution.
  • the neutralization can be carried out immediately after the esterification reaction has ended, or after removal of most of the excess alcohol by distillation. Preference is given to neutralization using aqueous sodium hydroxide immediately after ending of the esterification reaction at temperatures above 150° C. The water introduced with the aqueous sodium hydroxide can then be removed by distillation together with alcohol.
  • inventive diisononyl terephthalate mixtures can be used advantageously as plasticizer or part of a plasticizer composition in plastics or components of plastics, or as additive in paints or in coatings, or in adhesives or in components of adhesives, or in sealing compositions, or as solvent.
  • the inventive diisononyl terephthalates are more versatile than dialkyl terephthalates having 9 C atoms in the side chain which are isomerically pure, e.g. di-n-nonyl terephthalate and di-3,5,5-trimethylhexyl terephthalate, since they are liquid at room temperature and can therefore also be used in plastisol processes, which are quantitatively significant, and in which room-temperature application is possible only by using a liquid plasticizer phase. Since they are liquid even at low temperatures down to about ⁇ 70° C., and exhibit glass transition temperatures below ⁇ 70° C. or in some cases can reach temperatures as low as the glass transition temperature without any crystallization at all, they can moreover be pumped without difficulty even at very low temperatures and are therefore preferably suitable for industrial applications of this type.
  • inventive diisononyl terephthalate mixtures or else the mixtures of these with plastics preference being given here to PVC, PVB and PAMA, can also comprise further compounds which can be used as plasticizers.
  • these compounds which are particularly preferably esters, are by way of example the following:
  • dialkyl phthalates preferably having from 4 to 13 carbon atoms in the alkyl chain; trialkyl trimellitates, preferably having from 6 to 10 carbon atoms in the side chain; dialkyl adipates, preferably having from 6 to 10 carbon atoms; dialkyl terephthalates, in each case preferably having from 4 to 8 carbon atoms, in particular from 4 to 5 carbon atoms, in the side chain; 1,2-cyclohexanediacid alkyl esters, 1,3-cyclohexanediacid alkyl esters and 1,4-cyclohexanediacid alkyl esters, preference being given here to 1,2-cyclohexanediacid alkyl esters, in each case preferably having from 4 to 10 carbon atoms in the side chain; dibenzoic esters of glycols; alkylsulphonic esters of phenol preferably having an alkyl moiety which comprises from 8 to 22 carbon atoms; polymer plasticizers; glycerol esters, trialkyl cit
  • the composition particularly preferably comprises, alongside diisononyl terephthalates, in particular an alkyl benzoate having from 7 to 13 carbon atoms in the alkyl moiety, preferably isononyl benzoate, nonyl benzoate, isodecyl benzoate or decyl benzoate, or 2-propylheptyl benzoate. Particular preference is likewise given to a mixture composed of diisononyl terephthalates with dipentyl terephthalates.
  • the proportion of inventive diisononyl terephthalates in the mixture with other plasticizers is preferably from 15 to 95%, particularly preferably from 20 to 90% and very particularly preferably from 25 to 85%, where the proportions by weight of all of the plasticizers present give a total of 100%.
  • compositions mentioned composed of diisononyl terephthalate and of other plasticizers can be used as plasticizer composition in plastics and plastics compositions, in adhesives, in sealing compositions, in coatings, in paints, in plastisols, or in inks.
  • the inventive plastics compositions which comprise the diisononyl terephthalate mixtures according to the invention can be polymers selected from polyvinylchloride (PVC), polyvinylidene chloride (PVDC), polyacrylates, in particular polymethyl methacrylate (PMMA), polyalkyl methacrylate (PAMA), fluoropolymers, in particular polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyvinyl acetals, in particular polyvinyl butyral (PVB), polystyrenepolymers, in particular polystyrene (PS), expandable polystyrene (EPS), acrylonitrile-styrene-acrylate (ASA), styrene-acrylonitrile (SAN), acrylonitrile-butadiene-styrene (ABS), styrene-maleic
  • inventive compositions preferably comprise PVC or homo- or copolymers based on ethylene, on propylene, on butadiene, on vinyl acetate, on glycidyl acrylate, on glycidyl methacrylate, on methacrylates, on acrylates, or on acrylates or methacrylates having, bonded to the oxygen atom of the ester group, alkyl moieties of branched or unbranched alcohols having from one to ten carbon atoms, or on styrene, on acrylonitrile, or on cyclic olefins.
  • the inventive composition in the form of a grade of PVC preferably comprises suspension PVC, bulk PVC, microsuspension PVC or emulsion PVC. Based on 100 parts by weight of polymer, the inventive compositions preferably comprise from 5 to 200, with preference from 10 to 150, parts by weight of inventive plasticizer.
  • inventive compositions can comprise, alongside the constituents mentioned, further constituents, for example in particular further plasticizers, fillers, pigments, stabilizers, co-stabilizers, such as epoxidized soybean oil, lubricants, blowing agents, kickers, antioxidants or biocides.
  • further constituents for example in particular further plasticizers, fillers, pigments, stabilizers, co-stabilizers, such as epoxidized soybean oil, lubricants, blowing agents, kickers, antioxidants or biocides.
  • compositions composed of diisononyl terephthalates and of the abovementioned polymer materials can be used as plastics compositions, adhesives, sealing compositions, coatings, paints, plastisols, synthetic leather, floor coverings, underbody protection, textile coatings, wallpapers or inks, or for the production of these.
  • plastics products produced using the plasticizer compositions can be: profiles, gaskets, food-or-drink packaging, foils, toys, medical items, roof sheeting, synthetic leather, floor coverings, underbody protection, coated textiles, wallpapers, cables and wire sheathing.
  • Preferred application sectors from this group are food-or-drink packaging, toys, medical items, wallpapers and floor coverings.
  • DINTP Diisononyl Terephthalate
  • the degree of branching of the alcohol side chain of this ester was determined as XX.
  • the glass transition temperature (DIN “average”) was determined by differential scanning calorimetry (DSC) as ⁇ 83° C. No melting signals were detected.
  • the product can therefore be used without difficulty as plasticizer in plastisols, as shown by example 6.
  • the glass transition temperature (DIN average) was determined by DSC as ⁇ 76° C.
  • the degree of branching of the alcohol side chain of this ester was determined as XX.
  • the relatively high degree of branching of the alcohol used here is therefore itself sufficient to increase the glass transition temperature of the corresponding ester significantly, and thus also to increase its capability of reducing the glass transition temperature of the PVC to the extent that it remains flexible even at relatively low outdoor temperatures.
  • n-nonanol FLUKA was esterified with terephthalic acid and worked up as described above. When the product, whose ester content according to GC is >99.8%, is cooled to room temperature it solidifies.
  • the melting point was determined by DSC as 46° C., the incipient rise of the melting signal (“Onset”) being utilized for this purpose. No glass transition temperature was detected.
  • a plastisol was produced as follows using the inventive diisononyl terephthalate produced according to example 1:
  • the plastisol was again stirred with a spatula in the storage container and tested in the Z3 test system (DIN 25 mm) according to the operating instructions.
  • the test proceeded automatically by way of the above-mentioned software at 25° C. The following conditions were applied:
  • test data were automatically processed by the software after the test. Viscosity was shown as a function of shear rate. The test was carried out after a storage period of 2 hours in standard conditions of temperature and humidity.
  • Graph 1 shows the viscosity of the plastisol as a function of shear rate.
  • the plastisol has good processability, since the viscosities of the plastisol in the central shear rate range (10 s ⁇ 1 ) are relatively low and the incipient rise in the higher range of shear rate is relatively moderate.

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US20100305255A1 (en) 2010-12-02
CN101925571A (zh) 2010-12-22
CA2711680C (en) 2016-05-24
EP2234957A1 (de) 2010-10-06
JP2011510937A (ja) 2011-04-07
DE102008006400A1 (de) 2009-07-30
DK2234957T3 (da) 2014-07-21
PL2234957T3 (pl) 2014-08-29
WO2009095126A1 (de) 2009-08-06
JP5812605B2 (ja) 2015-11-17
KR101582699B1 (ko) 2016-01-05
EP2234957B1 (de) 2014-04-23
SI2234957T1 (sl) 2014-08-29

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